Unique Reactivity of (Arylimido)vanadium(V)–Alkyl Complexes with Phenols: Fast Phenoxy Ligand Exchange in the Presence of Vanadium(V)–Alkyls

Reactions of the aryloxo-modified (arylimido)vanadium(V) mono- or dialkyl complexes, V(NAr)(CH2SiMe3)2(OAr) or V(NAr)(CH2SiMe3)(OAr)2 (Ar = 2,6-Me2C6H3), with various phenols in C6D6 have been explored. The reaction of V(NAr)(CH2SiMe3)2(OAr) (1a) with ArOH in C6D6 did not take place at 25 °C even after 24 h, and the reaction affording V(NAr)(CH2SiMe3)(OAr)2 (2a) was complete after 50 h at 60 °C. In contrast, the reaction of 1a with C6F5OH took place rapidly at 25 °C, affording another monophenoxide, V(NAr)(CH2SiMe3)2(OC6F5) (1b), in addition to formation of the corresponding bis(phenoxide), V(NAr)(CH2SiMe3)(OAr)(OC6F5) (2b). The immediate ligand exchange was also observed when V(NAr)(CH2SiMe3)(OAr)2 (2a) was added to C6F5OH at 25 °C, affording 2b exclusively without reaction with the vanadium(V)–alkyl bond: further, subsequent reaction of 2b with C6F5OH or ArOH did not take place or was very slow at 25 °C. The exchange of 1a (in C6D6 at 25 °C) with various phenols (Ar′OH) proceeded in the order Ar′ = C6F5...

[1]  Shu Zhang,et al.  Design of vanadium complex catalysts for precise olefin polymerization. , 2011, Chemical reviews.

[2]  M. Tamm,et al.  1,2-C−H Activation of Benzene Promoted by (Arylimido)vanadium(V)-Alkylidene Complexes: Isolation of the Alkylidene, Benzyne Complexes , 2011 .

[3]  Wenjuan Zhang,et al.  (Imido)vanadium(V)-alkyl, -alkylidene complexes exhibiting unique reactivity towards olefins and alcohols , 2010 .

[4]  C. Redshaw.  Vanadium procatalysts bearing chelating aryloxides: structure-activity trends in ethylene polymerisation. , 2010, Dalton transactions.

[5]  Shu Zhang,et al.  Highly efficient dimerization of ethylene by (imido)vanadium complexes containing (2-anilidomethyl)pyridine ligands: notable ligand effect toward activity and selectivity. , 2010, Journal of the American Chemical Society.

[6]  K. Nomura.  Half-titanocenes containing anionic ancillary donor ligands as promising new catalysts for precise olefin polymerisation. , 2009, Dalton transactions.

[7]  Wen‐Hua Sun,et al.  Synthesis of (Arylimido)vanadium(V) Complexes Containing (2-Anilidomethyl)pyridine Ligands and Their Use as the Catalyst Precursors for Olefin Polymerization , 2009 .

[8]  Wen‐Hua Sun,et al.  Synthesis of (1-Adamantylimido)vanadium(V)-alkyl Complexes Containing a Chelate Alkoxo(imino)pyridine Ligand, and Reactions with Alcohols (ROH) That Proceed via Intermediates Formed by Coordination of ROH , 2009 .

[9]  Z. Guan.  Metal catalysts in olefin polymerization , 2009 .

[10]  Wenjuan Zhang,et al.  Facile Synthesis of (Imido)vanadium(V)−Alkyl, Alkylidene Complexes Containing an N-Heterocyclic Carbene Ligand from Their Trialkyl Analogues , 2008 .

[11]  Wenjuan Zhang,et al.  Reactions of an (Arylimido)vanadium(V)−Alkylidene, V(CHSiMe3)(N-2,6-Me2C6H3)(N═CtBu2)(PMe3), with Nitriles, Diphenylacetylene, and Styrene , 2008 .

[12]  M. Fujiki,et al.  Syntheses of Various (Arylimido)vanadium(V)–Dialkyl Complexes Containing Aryloxo and Alkoxo Ligands, and Ring-Opening Metathesis Polymerization Using a Vanadium(V)–Alkylidene Complex , 2008 .

[13]  S. Katao,et al.  Synthesis and Structural Analysis of (Arylimido)vanadium(V) Complexes Containing Phenoxyimine Ligands: New, Efficient Catalyst Precursors for Ethylene Polymerization , 2008 .

[14]  Jesús Cano,et al.  How to synthesize a constrained geometry catalyst (CGC) – A survey , 2007 .

[15]  Boonyarach Kitiyanan,et al.  Nonbridged half-metallocenes containing anionic ancillary donor ligands: New promising candidates as catalysts for precise olefin polymerization , 2007 .

[16]  K. Nomura,et al.  Synthesis of Various (Arylimido)vanadium(V)−Methyl Complexes Containing Ketimide Ligands and Reactions with Alcohols, Thiols, and Borates: Implications for Unique Reactivity toward Alcohols , 2007 .

[17]  H. Braunschweig,et al.  Constrained geometry complexes—Synthesis and applications , 2006 .

[18]  R. Schrock,et al.  A well-defined, silica-supported tungsten imido alkylidene olefin metathesis catalyst , 2006 .

[19]  Wei Wang,et al.  Notable Effects of Aluminum Alkyls and Solvents for Highly Efficient Ethylene (Co)polymerizations Catalyzed by (Arylimido)- (aryloxo)vanadium Complexes , 2006 .

[20]  H. Alt.  Metallocene complexes as catalysts for olefin polymerization , 2006 .

[21]  K. Nomura,et al.  A Stable Vanadium(V)-Methyl Complex Containing Arylimido and Bis(ketimide) Ligands That Exhibits Unique Reactivity with Alcohol , 2005 .

[22]  K. Nomura,et al.  Remarkable Effects of Aluminum Cocatalyst and Comonomer in Ethylene Copolymerizations Catalyzed by (Arylimido)(aryloxo)vanadium Complexes: Efficient Synthesis of High Molecular Weight Ethylene/Norbornene Copolymer , 2005 .

[23]  D. Stephan.  The Road to Early-Transition-Metal Phosphinimide Olefin Polymerization Catalysts , 2005 .

[24]  K. Nomura,et al.  A Vanadium(V) Alkylidene Complex Exhibiting Remarkable Catalytic Activity for Ring-Opening Metathesis Polymerization (ROMP) , 2005 .

[25]  Paul D. Bolton,et al.  Transition Metal Imido Compounds as Ziegler–Natta Olefin Polymerisation Catalysts , 2005 .

[26]  Guohua Liu,et al.  Neutral and Cationic Vanadium(III) Alkyl and Allyl Complexes with a Cyclopentadienyl-amine Ancillary Ligand , 2004 .

[27]  Christopher W. Jones,et al.  Toward single-site, immobilized molecular catalysts: site-isolated Ti ethylene polymerization catalysts supported on porous silica. , 2004, Journal of the American Chemical Society.

[28]  T. Marks,et al.  Synthesis, spectroscopy, and catalytic properties of cationic organozirconium adsorbates on "super acidic" sulfated alumina. "Single-site" heterogeneous catalysts with virtually 100 active sites. , 2003, Journal of the American Chemical Society.

[29]  S. Gambarotta.  Vanadium-based Ziegler–Natta: challenges, promises, problems , 2003 .

[30]  V. C. Gibson,et al.  Advances in non-metallocene olefin polymerization catalysis. , 2003, Chemical reviews.

[31]  G. Koten,et al.  Homogeneous vanadium-based catalysts for the Ziegler–Natta polymerization of α-olefins , 2002 .

[32]  B. Donnadieu,et al.  Cationic Vanadium(IV) Methyl Complexes [Cp2VMe(CH3CN)][B(C6H5)4] and [Cp2VMe(THF)][MeB(C6F5)3] , 2002 .

[33]  G. Yap,et al.  Stability of Metal−Carbon Bond versus Metal Reduction during Ethylene Polymerization Promoted by a Vanadium Complex: The Role of the Aluminum Cocatalyst , 2002 .

[34]  Y. Imanishi,et al.  Olefin Polymerization and Ring-Opening Metathesis Polymerization of Norbornene by (Arylimido)(aryloxo)vanadium(V) Complexes of the Type VX2(NAr)(OAr`). Remarkable Effect of Aluminum Cocatalyst for the Coordination and Insertion and Ring-Opening Metathesis Polymerization , 2002 .

[35]  G. Yap,et al.  Stability of Trivalent Vanadium Alkyl and Hydride Supported by a Chelating Phosphinimido Ligand , 2001 .

[36]  J. Gladysz.  Frontiers in Metal-Catalyzed Polymerization: Designer Metallocenes, Designs on New Monomers, Demystifying MAO, Metathesis Déshabillé. , 2000, Chemical reviews.

[37]  R. Waymouth,et al.  Group 4 ansa-Cyclopentadienyl-Amido Catalysts for Olefin Polymerization. , 1998, Chemical reviews.

[38]  R. Mülhaupt,et al.  Novel polyolefin materials via catalysis and reactive processing , 1998 .

[39]  V. Murphy,et al.  Low-Coordinate (Arylimido)vanadium(V) Alkyls: Synthesis and Reactivity of V(NAr)(CH2Ph)3 (Ar = C6H3-2,6-Pri2) , 1997 .

[40]  W. Kaminsky,et al.  Metallocenes for Polymer Catalysis , 1997 .

[41]  J. Cole,et al.  Novel µ-methyl complexes of vanadium and their relevance to bimolecular deactivation of homogeneous imidovanadium polymerisation catalysts , 1997 .

[42]  J. Arnold,et al.  Synthesis and Reactivity of a Vanadium(III)−Methyl Complex Stabilized by Hexamethylsilazanate Ligands , 1996 .

[43]  David Fischer,et al.  Stereospecific Olefin Polymerization with Chiral Metallocene Catalysts , 1995 .

[44]  G. Solan,et al.  CYCLODIVANADAZENE ALKYL AND ARYL COMPLEXES , 1994 .

[45]  A. Orpen,et al.  Stable alkylvanadium(V) compounds containing bulky imido and amido ligands , 1990 .

[46]  J. H. Teuben,et al.  An Alkylidene Complex of Vanadium: Synthesis and Structure of Cyclopentadienyl[bis(dimethylphosphino)ethane](neopentylidene)vanadium(III) , 1989 .

[47]  J. Kaub,et al.  Darstellung und Struktur der zweikernigen tert-Butyliminovanadium(IV)-Komplexe: [(tC4H9N)2V2Cp2X2] (X = OtC4H9, Cl) , 1988 .

[48]  J. Lichtenhan,et al.  Complexes of (arylimido)vanadium(V). Synthetic, structural, spectroscopic, and theoretical studies of V(Ntol)Cl3 and derivatives , 1987 .

[49]  K. G. Caulton,et al.  Paramagnetic monocyclopentadienyl hydrocarbyl and borohydride compounds of vanadium(II) and vanadium(III). Synthesis, structure, and reactivity , 1987 .

[50]  K. G. Caulton,et al.  Cyclopentadienylvanadium(III) and -vanadium(II) Methyl, Phenyl, and Borohydride Compounds , 1985 .

[51]  Y. Doi,et al.  Synthesis of a propene—methyl methacrylate diblock copolymer via “living” coordination polymerization , 1985 .

[52]  G. Duyne,et al.  Preparation of Group 4B complexes containing tri-tert-butylmethoxide (tritox), a steric cyclopentadienyl equivalent , 1984 .

[53]  F. Preuss,et al.  Alkylvanadium(V)-Verbindungen Darstellung und NMR-spektroskopische Untersuchungen/Alkylvanadium(V) Compounds Synthesis and NMR Spectroscopic Studies , 1982 .

[54]  Y. Doi,et al.  "Living" Coordination Polymerization of Propene Initiated by the Soluble V(acac)3-Al(C2H5)2Cl System , 1979 .

[55]  D. Christman,et al.  Reactivities of Nonconjugated Dienes Used in Preparation of Terpolymers in Homogeneous Systems , 1968 .

[56]  W. Carrick,et al.  Transition metal catalysts. VIII. The role of oxygen in ethylene polymerizations with the AlBr3‐VXn‐Sn(C6H5)4 catalyst , 1962 .

[57]  G. Bier,et al.  Polymerisation von äthylen und propylen zu amorphen copolymerisaten mit katalysatoren aus vanadiumoxychlorid und aluminiumhalogenalkylen , 1962 .

[58]  G. Sartori,et al.  Ethylene–propylene copolymerization in the presence of catalysts prepared from vanadium triacetylacetonate , 1961 .

[59]  F. Rugg,et al.  Transition Metal Catalysts. I. Ethylene Polymerization with a Soluble Catalyst Formed from an Aluminum Halide, Tetraphenyltin and a Vanadium Halide1 , 1960 .

[60]  W. Carrick.  MECHANISM OF ETHYLENE POLYMERIZATION WITH VANADIUM CATALYSTS , 1958 .

[61]  P. Walden.  Stereochemie und Technik , 1925 .